Polyarylmethane hydrazinium compounds



United States Patent 3,112,326 POLYARYLMETHANE HYDRAZINIUM COMPOUNDS Bernard Rudner, Pittsburgh, and Charles W. Wieneke,

Lancaster, Pa., assiguors to W. R. Grace & Co., New 5 York, N.Y., a corporation of Connecticut No Drawing. Filed June 19, 1959, Ser. No. 821,390

4 Claims. (Cl. 260391) This invention relates to polyarylmethane compounds. In one specific aspect, it relates to salts which maybe described as diand triarylmethane hydrazinium compounds.

Probably the best known polyarylmethane compounds are the triphenylmethane dyes, e.g., Malachite Green, Crystal Violet, the Victoria Blues, Wool Green, the Patent Blues and the Brilliant Indocyanines. These corn pounds are best known for the intensity and brilliance of the color they bestow on fibers and the strength of shade their lakes and toners possess. The simple representative triphenylmethane dyes are frequently made by condensing an aromatic aldehyde, such as benzaldehyde, with an aromatic amine to form the leuco base. Subsequent oxidation of the colorless base in an acid medium, suitably with lead dioxide or manganese dioxide, yields the dye.

E CHO NCH CH: CH;

Colorless Leuco PbO:

Green Dye versibly to its colorless carbinol form.

Colored Dye HClI lNaOH herein.

(CH N-CHi- N(CH3)2 Michlcrs Base Colorless Carblnol or Colored Base N (CH3) THC]. I

Auramine 00 N (CH3):

Michlers Hydrol HOaS SO H Leuco. Green 8 ID i PbOg 69 (CH3)2N Cl =N (CHa)2 HO as S 0 a I Wool Green S Michlers Ketone C O OH lPOCla 900C CH;

Monochrome We have discovered certain novel polyarylmethane hydrazinium salts possessing remarkable fungicidal and bacteriocidal properties. These novel salts are most conveniently prepared by the action of chloramine or hydroxylamine-o-sulfonic acid on tertiary-amino containing polyarylmethane compounds.

It is, therefore, an object of the present invention to provide a new generic class of diand triphenylmethane compounds useful as fungicidal and bacteriocidal agents.

The novel hydrazinium compounds of our invention have the general formula:

The remaining two valences of the central carbon atom are satisfied by =H H and OH, =0, =NH, -H

and

OH and R @R yrs.

Q may be NRR or N(NH )RR, each R in the above structure may be lower alkyl or benzyl and R may be H, OH or NRR. The phenylene groups in the above formulae may bear the usual substituents found on benzene rings, i.e. halo, alkyl, sulfonic acid, carboxylic acid etc. Since the primary utility of these compounds resides in the cationic portion of the molecule, we do not wish to be bound by any arbitrary limitations on the nature of the anions A and X save that the number of cations present must balance the anionic charge.

Our compounds can be made by the N-amination of the leuco base, the color base or the dye proper. The same interconversions among the leuco and color bases and the dye itself characteristic of the triphenylrnethane dye series are undergone by their hydrazinium counterparts. Thus it is possible to N-aminate the most readily available or chemically convenient species and convert it to the desired species as necessary. N-amination is most conveniently accomplished by the action of chloramine or hydroxylamine-o-sulfonic acid on a tertiary amine as shown in the examples that follow. Since the reaction of chloramine with a tertiary-amino-containing polyarylmethane compound yields the corresponding hydrazinium chloride and similarly the reaction of hydroxylamine-o-sulfonic acid gives the corresponding hydrazinium sulfate and bisulfate, metathesis is necessary to substitute another anion for the chloride or sulfate ions. Such a substitution can be readily accomplished by standard techniques and broadens the utility spectrum of our novel compounds.

The compositions of this invention are useful as antioxidants and as powerful biocides particularly as bacteriocides and fungicides. Our novel compounds are also useful as biocidal and bacteriological stains and as basic dye-stuffs and dye-stuff intermediates.

The scope and utility of our invention is further illustrated by the following examples:

4 EXAMPLE 1 A chloramine-ammonia generator was constructed according to the teachings of Sisler et al., US. Patent 2,710,- 248, discussed above. Using such a generator, chloramine was passed into a solution of 25 g. of leuco Crystal Violet in 1000 ml. of chloroform for about a half hour. After filtration from the resultant ammonium chloride, the filtrate was evaporated to dryness leaving a residue weighing 29.9 g. The unreacted amine was extracted with methyl alcohol leaving 20 g. of 1,1-dimethyl-l-[4-(p,p tetramethyldiaminobenzhydryl) phenyl]hydrazinium chloride melting l63 C. and containing 8.01% chloride ion or 96.5% pure. The preparative sequence is shown below:

[(0Hom orr own, l

H (CHQzNQ-C-Q-lf-(Clh):

EXAMPLE II Using the generator of Example I, excess chloramine was passed into a solution of 50 g. of Crystal Violet dissolved in chloroform. After the reaction had been completed, filtration gave 29 g. of solid and 37 g. additional solid was obtained by evaporation of the filtrate. Each residue was extracted with isopropyl alcohol to separate the product from the ammonium chloride present. Combination of the new residues obtained from the alcohol extracts gave 30 g. of 1,1-dimethyl-1-[4-(alpha-hydroxy- P,P' tetramethyldiaminobenzhydryl)phenylJhydrazinium chloride (the color base) melting 160-164 C. The pure product analyzed: 66.98% C, 7.71% H, 12.86% N and 8.35% C1. Calculated for C H ClN,O: 67.20% C, 7.75% H, 13.06% N and 8.26% Cl. Treatment of the color base with an equivalent amount of hydrochloric acid converted it to the dye proper, 1,1-dimethyl-l-[4- (alpha (quinone p dimethylimonium) 4 dimethylaminobenzyl) )phenyl]-hydrazinium dichloride, as shown Color Base a) I NH Dye Proper EXAMPLE III A solution of 25 g. of p-hydroxybenzylidene-bis-(p,p'- dimethylaniline) dissolved in one liter of chloroform was treated with gaseous chloramine made from 12 g. of chlorine according to the general method of Example I. After removal of most of the ammonium chloride by filtration, evaporation of the solvent gave 22.9 g. of residue from which g. of unreacted amine was recovered. The 7.9 g. of crude product remaining was separated from about 1.0. of ammonium chloride present by fractional crystallization from methyl alcohol-ethyl acetate. Further trituration with ethyl acetate gave 4.5 g. of 1,1-

dimethyl 1 [4 (p, hydroxy-p-dimethylaminobenzhydryl)phenyl]hydrazinium chloride melting with decomposition ca. 172 C. and having the following structure:

6 phenylmethane 4,4 bis-(alpha,alpha-dimethylhydrazinium)sulfate having the formula shown:

H 10 After recrystallization, the product melted 193-194 C. H0C-N(0Ha)z and had the following analysis: 11.76% N and 6.97% S.

L Calculated for'C H N SO 12.22% -N and 6.99% s. C1 The corresponding chloroplatinate salt was prepared I, and analyzed. Found: 36.27% C; 4.17% H; 7.01% N; and 25.24% Pt. Calculated for C H N PtCl 35.85% N('CH3), C; 3.92% H; 7.27% N; and 25.33% Pt.

, *In addition to illustrating the preparation of a hydra- EXAMPLE 1V zinium sulfate, this example shows the formation of a dihydrazinium product by the use of excess hydroxyl- Usmg a generatgr construe? g to Example amine-o-sulfonic acid. Such di-N-amination reactions I, a solution of 50 g. of Auramme dissolved in chloroform are geneml and will result when a compound containing was treated with excess chloramine. After filtration from a Second tertlaryamino group is exposed to (the action of the ca. 18 g. of ammonium chloride formed, the filtrate excess N amlnatlng agent This will more frequently was evaporated to dryness and the extracted Wlth occur with hydroxylamine-o-sulfonic acid than with chlorether to remove tars and reacted Auramme' There 25 amine because the initial hydrazinium chloride formed by obtamfidfisfi of 'F the reaction of chloramine is usually insoluble in the hyalPha-lmlnobenzynphenyllhYdraZmmIP chlonde meltmg drocarbon or hydrocarbon-like reaction medium. When T Tlfeatment of s.mau p p the product hydroxylamine-o-sulfonic acid is used, both it and the with saturated aqueous solutions of PlCIlC acid and potashydrazinium Sulfate formed are usually Soluble in the sium hexafiuorophosphate gave the corresponding hy alcohol solvent customarily employed favoring further zinium picrate (M.P. 83-86 C.) and hexafluorophosphate N aminallon (M.P. l28-l32 C. with charting) respectively. The structural formula of the latter is shown below: EXAMPLE VII The object of this example is to illustrate the bacterio- (CH3) 1N-0-N-4CHQ PF static and fungistatic activity of some representative com- Q l pounds of our invention. Each compound was tested for bacteriostatic activity against Mzcrococcus pyrogenes var. E A LE V aureus and for fungistatic activity against Canidida albi- 40 cans, M. gypseum and Chaetomium globosum by means A solution of 25 g. of p,p'-methylene-bis-(N,N-dimethof the Oxford cup method using Zephiran as the control. ylaniline) dissolved in 500 ml. of chloroform was treated Each of the experimental compounds was prepared as a With gaseous chloramine made from 19 g. of chlorine 0.1%, 0.01% and 0.001% weight/volume solution or susaccording to the general method of Example I. The resipension in distilled water. The pH was adjusted to 7.0 due obtained by evaporation of the filtrate (after removal by the addition of dilute hydrochloric acid or sodium of ammonium chloride) was carefully triturated with hot hydroxide. Flasks containing 100 ml. of the appropriate benzene. The yield of product after filtration was 16.5 g. sterile melted medium were inoculated with 0.1 ml. of The 1,1-dimethyl-l-[4-(4-dimethylaminobenzyl)phenyl] viable 18-24 hour broth cultures of the respective orhydrazinium chloride thus obtained melted with decomganism. After thorough mixing, 13 ml. quantities of the position at 195-197 C. and analyzed for 11.3% chloride inoculated media were transferred aseptically to sterile ion or 97.5% pure. Treatment of a small portion of the Petri dishes and allowed to solidify, after which the plates product with aqueous picric acid gave the corresponding were refrigerated overnight. Nutrient agar was used for hydrazinium picrate melting 147-150 C. shown below: the bacteria and Sabourands dextrose or potato agar for NO: (CHa)zN-CH2ITT(CH3) 2] NH: OzN

N02 EXAMPLE VI (50 the fungi. The following morning, three sterile stainless steel Oxford cups (10 mm. diameter) were placed equi- To a .nllxture of of benZyhdene'b1S'(NN'd1' distantly over the surface of the medium in each plate, methylamlwfi 50 of methanql 50 of a after having been slightly warmed in the Bunsen flame. rated solution of sodium hydrox de in methanol, there The plates lcontainlng the cups were refrigerated for was q of hydroxylamme'o'sulfomc 35 proximately two hours to form a tight seal between cup 9 m 25 of safne solvent- A mmal and medium. Following refrigeration, the cups were vigorous reaction had subsided, the reaction mixture was filled approximately three fourths full (Q7 ml) with the heated for y mmutes filtered and sepa-ratcd sohds various solutions to be tested. Each central and experiwashfad well with methanol- The combmed filtrates and mental solution was tested on duplicate plates on two Wa$h1ng$ WeIe eflaporafled d y and the residue different days, giving a total of four readings for each taken up in a mixture of Water and ether- Aftel pa asolution tested. The plates containing C. albicans and tion, the aqueous layer was treated with Norite and evap- M. pyrogenes were incubated at 37 C. for 24 hours. orated to dryness. The new residue was taken up in The plates containing M. gypseum and Ch. globosum were isopropyl alcohol and crystallized by the addition of ethyl incubated at room temperature (ca. 25 C.) for 3 or 4 acetate. There was obtained 2 g. (a 24% yield) of tridays. At the end of the incubation period, the plates were carefully examined and the diameter of the zone of inhibition of microbial growth surrounding each up was measured. A notation of the degree (complete or partial) of inhibition of growth was also made in the case of C. albicans and M. gypseum. The results obtained were averaged and a summary of the tests are tabulated below:

Zone Inhibition, a Measure of Bacteriostatic and Fungistatic Activity Test material Conccn- C. albi- M. gyp- Ch. glo- M. pyrotration cans seum bosum genes Zephiran (control). 0. 001 10 13 12 13 0.01 12 15 (p) 19 0.1 17 26 28 23 Hydraziniurn chloride of Example I 0.001 l0 10 10 10 0.01 14 (p) 10 l1 11 0.1 14 14 (D) 17 Hydrazinium chloride of Example II... 0.001 12 10 1O 0. 01 21 26 (p) 14 17 0. 1 23 24 20 (1)) indicates partial inhibition.

8 We claim: 1. Compounds having the formula NH; L

wherein 2 is a member selected from the group consisting of =H =NH, and

References Cited in the file of this patent UNITED STATES PATENTS 2,955,108 Omietanski Oct. 4, 1960 

1. COMPOUNDS HAVING THE FORMULA 